Azo dyes



Patented July 15, 1941 UNITE Hes grat s Azonrns Swanie S. Bossander, Wilmington, DcL, Donovan E. Kvalnes, Perms Grove, N. .L, and Chiles E. Sparks, Wilmington, DeL, assignors to E. I.

du Pont de Nemours &;.-,Qompany, Wilmington,- V DcL, a corporation of Delaware No Drawing. Application September 12, 1939,

Serial N0. 294,430

17 Claims. (creat n This invention relates to azo dyes, to direct dyes, to dyes after-treated with formaldehyde, and to metallized dyes.

Direct azo dyes are those which dye the cloth directly from a water bath without subsequent treatment to bring out the color. Many examples of such direct dyes are recorded inthe literature of the trade. These direct colors are generally-substantive to cotton and other forms of cellulose and regenerated cellulose, giving bright shades, but having only moderate fastness to light. These direct colors show considerable loss in strength and impart an undesirable stain to associated uncolored or difierently colored fibers when they are washed. Direct colors with good washing fastness, and which will not stain associated'fibers are desired by the trade, because of their low cost and ease of application. In order to provide dyes which do not have poor fastness to washing the art has been forced to use thed'eveloped colors, wherein an intermediate, usually a direct dye, is azotized on the fiber and developed withsuitable coupling compounds. These, so-called developed or diazo colors are generally'faster to washing than the'correspond ing direct colors, but they are duller, more costly, more costly to apply as such dyeings require much time and labor and the dyeings change shade during development.

It is an object of this invention to provide a class of colors having the-simplicity of application and constant, bright shade of the direct colors, and washing fastness superior to the direct' colors; Anotherobject of the invention is to provide methods of applying the. colors and of increasing their lightfastness,

The objects of the invention are attained in, general by applying to the material to be dyed, compounds represented by the formula This compound is then tetrazotized and coupled with twomol equivalents of .a compound A- The resulting compound .rf Y 1 A+Y+-X+Y A when separated from themedium by suitable means is soluble in Water. Such solutions may be used as dyebaths in which dyeable materials may be immersed anddyed. Further objects of the invention are attained by treating such dyeings with asolution of formaldehyde, with solutions oficertain soluble salts of metals or with both'of said solutionswhereby new and improved dyeings areobtained. I r

In the formula I the symbol A is a meta-dihydroxy benzene rep resented by the formula in which R is one of a group consisting of hy- The symbol X stands fora diphenyl compound having amino groups in the benzene nuclei which are ortho, meta or para to a bridging group. These compounds are represented by the general formulae nd HiN V NHz' (Ron in which Q is a straight or branched chain alkylene radical having 1 to 10 carbons, a mono-hydroXy-alkylene radical having 3 to -7 carbons wherein the hydroxyl group is attached to a carbon atom other than one which is directly attached to S or Q, or two alkylene radicals containing l to 4 carbons connected together by an oxygen bridge as in an ether; R is hydrogen, alkyl, alkoxy, halogen, carboXy or sulfonic acid;

= and the W5 are integers of 1 to 4. The R. groups in a given diphenyl compound may be alike or unlike.

The symbol Y stands for primary arylamines oi. the benzene and naphthalene series as fol wherein R" is methyl or carboxyl, R represents one or any combination of the same groups as R in the X compounds, 11 is 1 to 4 and amino may be in any position of the benzene ring.

(b) Amino benzenes which are represented by the formula wherein R is one or any combination of the group consisting of hydrogen, alkyl and alkoxy, n is 1 to 4, and R groups may be substituted in any position of the benzene ring except that occupied by -H;

(c) Naphthylamines represented by the formula wherein m is 1 or 2, and the R groups may be substituted in any positions of the several rings except that occupied by -H; and

(d) 1- and Z-amino-naphthol sulfonic acids represented by the formula as: Y

sisting of and A slurry was made by mixing 122 parts of 1,2-di(4'-amino-phenoxy) ethane with 5000 parts of water and adding 91 parts of hydrochloric acid as a 30% solution. The mixture was iced to 0 C. and 69 parts of 100% sodium nitrite were added as a 30% solution. Tetrazotization was carried out at 0-5 C. for one-half hour'with a faint excess nitrite.

A slurry was made by mixing 360 parts of 2-(3-amino benzoyl amino)-5-naphthol-7-sulfonic acid and 17 parts of 100% ammonia as a water solution or sufiicient annnonia to make a complete solution which was alkaline to Brilliant yellow. Then 15 parts of sodium bicarbonate were added and the solution was iced to 0 C. Finally 265 parts of sodium carbonate were added.

The tetrazo was slowly added to the alkaline solution of the coupling component whilst maintaining a temperature of 0-5 C. and an excess of 2-(3'-amino benzoyl amiino)-5-naphthol-7- sulfonic acid. The suspension was maintained distinctly alkaline to Brilliant yellow paper, stirred for one hour after the addition of the tetrazo, then heated to 70-430 C. and finally salted (5%) with sodium chloride and filtered.

The filter cake was stirred into 4,000 parts of water until a smooth slurry was obtained, iced to 10 C. and parts of 100% hydrochloric acid as a 30% solution were added. A solution containing 69 parts of 100% sodium nitrite as a 30% solution was added. Tetrazotization was completed at 10-12 C. in about one hour with a distinct excess of nitrite.

A solution was made bystirring 132 parts of 1,3-dihydroxy benzene into 2,500 parts of water. The solution was iced to 0 C. and 220 parts of sodium carbonate were added.

The tetrazo was slowly added to the alkaline solution of 1,3-dihydroxy benzene. There was an excess of 1,3-dihydroxy benzene and the suspension was alkaline to Brilliant yellow. The suspension was stirred one hour after the addition of the tetrazo, heated to 70-80 C., salted slowly with 10% of sodium chloride and filtered. The precipitate was dried at 80-85 C. in an oven and was a powder having a brownish-red appearance.

tervals.

Ihe compound is represented bythe formula y a =CN OH N=N -OH Rayon was dyed and after-treated as follows. A solution was made by dissolving 0.2 gram of the product in 50 cc. of water at 190-200 F. and adding 0.4 gram of sodium carbonate to S OaNQ assist the solution. The solution was diluted After-treatment in a fresh bath The rinsed dyeing from the above operation was entered into 500 cc. of water at 130-140 F. Then approximately cc. of a 10% formaldehyde solution (25 cc. of approximately 37% formaldehyde by weight diluted to 250 cc. with water) were added. The bath was held at this temperature for twenty minutesand the dyeing was removed, rinsed and dried.

After-treatment in the dye bath An alternative after-treating process which is the preferred procedure because of its economy and ease of application was carried out as follows.

At the end of the dyeing period 10 cc. of 10% formaldehyde solution was added to the dye bath at bath temperature. After twenty minutes the dyeings were removed, rinsed and dried.

A dyeing with a bright yellow scarlet shade was obtained which showed good discharge properties and better fastness to washing than the direct dyeing. Y

EXAMPLE 2 v I A slurry was made by mixing 138 parts of l,2-di(4-amino Dhenyl thio) ethane with 5000 parts of water and then adding 91 parts of 100% hydrochloric acid as a 30% solution. The mixture was iced to 0 C. and 69 parts of 100% sodiuml nitrite were added as a 30% solution. Tetrazotization was carried out at 0-5 C. for one-half hour with a faint excess nitrite.

A slurry was made by mixing 360 parts of Z-(P-amincv benzoyl amino) -5-naphthol-'7-sulfonic acid and 5,000 parts of water. The compound was dissolved by adding 17 parts of 100% 40 solution of 1,3-dihydroxy benzene.

ammonia as a water solution or sufficient am- OH monia to make a complete solution which was alkaline toBrilliant yellow. Then parts of 1; sodium bicarbonate were added and the solu tion was iced to 0 C. Finally 265 parts of sodium carbonate were added. 7 The tetrazojwas slowly added to the alkaline solution of the coupling component whilst mai'n- 20 taininga temperature of 05 C. and an excess of 2-(4'-amino benzoyl amino)-5-naphthol-7- sulfonic acid. The suspension was maintained distinctly alkaline to Brilliant yellow paper, stirred for one hour after the addition of the tetrazo then heated to 70-80 C. and finally salted (5%) with sodium chloride and filtered.

The filter cake was stirred into 4,000 parts of water until a smooth slurry was obtained, iced to 10 C. and 115 parts of 100% hydrochloric acid were added as a 30% solution. A solution containing 69 parts of 100% sodium nitrite as a 30% solution was added. Tetrazotization was completed at 10-15 C. in about one hour with a distinct excess of nitrite.

A solution was made by stirring 132 parts of 1,3-dihydroxy benzene into 2,500 parts of Water. The solution was iced to 0 C. and 220 parts of sodium carbonate were added.

The' tetrazo'was slowly added to the alkaline There was an excess of 1,3-dihydroxy benzene and the suspension was -maintained alkaline to Brilliant yellow. The suspension was stirred one hour after the addition of the tetrazo, heated to- 70-80 C., salted slowly (10%) with sodium chloride and filtered. -The' filter cake was driedat- 808 5 C. in an oven giving a dry powder;

having a brownish. red appearance. The compound is represented by the formula NaOsS- A dyeing was made and after-treated in- 'a manneri'similar to that described in Example 1. The dyeing was a bright red shade having excellent fastness to washing and good discharge properties. The fastness to washing was better than the direct dyeing.

EXAMPLE 3 A mixture containing 122 parts of 1,2-di(4'- amino-phenoxy) ethane, 5,000 parts of water and 91 parts of 100% hydrochloric acid as a 30% present.

To a slurry containing 230 parts of 1-(3'- amino-phenyl)-5-pyrazolone-3-carboxylic acid and 5,000 parts of water, 106 parts of sodium carbonate were added and the mixture was stirred until complete solution was obtained which was alkaline to Brilliant yellow paper. Then 265 parts of sodium carbonate were added and the solution was iced to C.

The tetrazo was slowly added to the cold alkaline solution of the coupling component whilst maintaining the temperature at 0-5 C. There was an excess of 1-(3-amino phenyl)--pyrazo1one-3-carboxylic acid and the suspension was alkaline to Brilliant yellow. After the addition of the tetrazo the suspension was stirred one hour, heated to 70-80 0., salted with sodium chloride, filtered and the filter cake was dried in an oven. The dry powder was red orange in appearance. The coupling component was 1,3-dihydroxy benzene and was used in the form described in the preceding examples.

The compound is represented by the formula HOQN=N- A dyeing was made and after-treated in a manner similar to that described in Example '1. A bright dyeing having a bright orange shade and showing excellent fastness to washing was obtained.

EXAMPLE 4 A slurry was made by stirring 122 parts of 1,2- di(4-aminophenoxy) ethane into 5,000 parts of water and 91 parts of 100% hydrochloric acid as a solution were then added. The mixture was iced to 0 C. and 69 parts of 100% "sodium nitrite as a 30% solution were added. Tetrazotization was carried out at 05 C. for one-half hour with a faint excess of nitrite,

A slurry containing 410 parts of 2-(4'-amino- 3'-sulfo-phenylamino) 5 naphthol 7 sulfonic acid and 5000 parts of water was made and then 250 parts of sodium carbonate were added to make complete solution. The solution was iced to 0 C. 265 parts of sodium carbonate were added. The tetrazo was slowly added to the alkaline solution of the coupling component whilst maintaining a temperature of 0-5 C., an excess of 2-(4'-amino-3-sulfo-phenylamino) 5 naphthol-7-sulfonic acid, and a distinct alkalinity to Brilliant yellow. The mixture was stirred one hour after the addition of the tetrazo, heated to '70-80 C., salted (15%) with sodium chloride and filtered.

The filter cake was stirred with 4,000 parts of water until a smooth slurry was obtained, iced to 10 C. and then 140 parts of 100% hydrochloric acid as a 30% solution were added. A 10% solution containing 69 parts of 100% sodium nitrite was added and tetrazotization was carried out at 10-15 C. for one hour with a distinct excess of nitrite.

A solution containing 132 parts of 1,3-dihydroxy benzene in 3,000 parts of water was made, iced to 0 C. and then 300 parts of sodium carbonate were added.

The tetrazo was slowly added to the alkaline solution of 1,3-dihydroxy benzene having present an excess of 1,3-dihydroxy benzene and having the suspension alkaline to Brilliant yellow. The mixture was stirred one hour after the addition of the tetrazo, heated to 70-80 C., salted 15%) with sodium chloride and filtered. The filter cake was dried at 85 C. in an oven. The dry powder was blue black in appearance. I

H COONa The compound is represented by the formula NaOaS N=N OCHOH'O -N=N e QH HO I NH- S OaNa SOsNa HOQM A dyeing was made and after-treated in a manner similar to that described in Example 1. A br ght dyeing in a bright rubine shade was obtamed which showed excellent fastness to washmg.

EXAMPLE 5 NaOaS A dyeing was made and after-treated in a manner similar to that described in Example 1. This dyeing was a bright scarlet shade which showed excellent fastness to washing.

place of 410 parts of 2-(4-amino-3"-sulfophenylamino) -5-naphthol-'l-su1fonic acid.

The final product is represented by the for.-

' mula v o' (I? g NH so3Na NaOa NH-C' N= NOO omcHcHm-ON I l N=N .OB N=N EXAMPLE 6 A dyemg was made and after-treated in a The procedure of Example 4 was followed, substituting 272 parts of 1,6-di-(4'-amino-phe noxy) -hexane for 122 parts of 1,2-di-(4'-aminophenoxy) -ethane and 371 parts of 2-(3'-aminobenzoylamino)-5-naphthol-'7-sulfonic acid for 410 parts of 2-(4'-amino-3'-sulfo-phenylamino) l O -Q A dyeing was made and after-treated ina 40 manner similar to that describednin Examplel. This dyeing was a scarlet shade whichshowed excellent fastness to washing.

EXA PLE 7 The procedure of Example followed, substituting 259 parts of 1,3-di-(4'-an 1inophenoxy) propanol-Z for 122 parts of 1,2-'di-'(4'-aminophenoxy),-ethane and 371 parts of- 2-(-i-amino-' benzoylamino)-5-naphthol-7-sulfonic 7 acid manner similar to that described in Example 1. This dyeing was a scarlet shade which showed 20 excellent washing fastness.

It is to be understood that the invention is not limited to the specific procedures'described inthe above examples since modifications, well known to the art, can Ice-applied with satisfac- 2 tory results; Many other similarproducts can be prepared by such methods and suitable modifications thereof. a

Other illustrations of the invention are shown in the following table. The products listed in the table are prepared by methods similar to those set forth in the foregoing examples. The "double arrowsin the table indicate that two 45 mols of the compounds toward which the arrows point were coupled with the tetrazotized compound from which the arrows proceed. Dyeings with these compounds were bright and they had the new improved properties of the comin 50 pounds described in the examples.

naphthol-7-sulfonic acid, 2-[4-(4".-amino-benzoyl)-amino]--naphthol-'7-sulfonic acid and 2(4-amino 3' sulfo-phenyl) 5-naphthol-7-sulfonic acid.

The preferred embodiments of the invention sulfate. 7 For example, the after-coppering operation may be carried out by either'of the procedures outlined in Example 1 for'theeftertreatment with formaldehyde, by using a'solution containing a 5% solution of hydrated cupric sulfate equal in amount: to the formaldehyde used in the preceding step. .In both casesthe operationis. allowed to continue for twenty min utes, or for such time as is necessary to metallize the dyeing, at theend .of which time the treated dyeings are removed, rinsed and dried.": The after-coppering may replace the formaldehyde treatment,- but both after-treatments are preferred where the best light fastness as well as washing fastness is desired. After-treatmentwith both form-aldehyde and metal salts may be done either in the dye bath or in a fresh bath. When a fresh formaldehyde bath is used and the dyeing is treated for a sufiicient time to form the formaldehyde compound, the metal salt may beadded and 'thetreatment continued for an interval of time. The dyeings are then removed, rinsed and dried. Similar results are obtained by reversing the order of adding the after-treating reagents, that is, by adding the metal salt solution first, treating for the necessary time, and then adding the formaldehyde solution.

After treating the dyeing for about twenty min- 7 utes, they are removed, rinsed and dried.

The described method of restricted to the precise concentrations, temperatures and intervals of treatment specified in the examples since these details can be variously modified as will be understood by those skilled in the art. For example, the after-treatments with formaldehyde or metal salts may be carried on for longer or shorter periods and at higher or lower temperatures than those specified in the illustrations. Any treatment which will form a formaldehyde complex with the dyeingor one of the described metal complexes with the dyeing, as the case may be, produces the improved results with thedyes described. The exactycomosition of the described formaldehyde .,.and metal complexes is unknown to us, but from our investigationsit is our present belief that formaldehyde and metal complexes are formed.

7 In the specification and claims alkylrefers to. straight and branched aliphatic groups and, ,7 70

alkoxy refers ,to the corresponding alkoxy groups. The sulfonicacid and carboXyl' g oups in the dyes;may be the salts of any of the alkali metals and may, be. produced by making the coupling media basic with the corresponding alkalis. The acid forms may also be made by treating'the dyeing is typical but 7 it is to be understood that the invention is not that directly attached to O-- or S- and .mula

' formulae alkali metal salt forms with acids by methods well known in the art.

Water-soluble metal salts of various metals can be used for metallizing the dyeings, those having atomic weights between and 65 being the most suitable. Asexamples of such metals copper, chromium, nickel, cobalt and iron are mentioned. Either water-soluble salts of inorganic-or organic-acids can be used such as sul fates-, halides, formates and acetates, for ex ample copper-sulfate, nickel sulfate, chromium chloride, copper' 'formate, copper acetate and many other water soluble metal salts offinorganic-ari'd organic acids. 1

-' The compounds" of the ihveiitionin-the-form of the'ir alkali metal salts give dyeings on ce11ulosic fibers which are equal to and superior in washing fastness to direct colors and they are in general more convenient and less costly to apply than developed colors.

From the foregoing disclosure it will be recognized that the invention is susceptible of modification without departing from the spirit and scope thereof and it is to be understood that the invention is not restricted to the specific il1ustrations thereof herein set forth. Weolaim:

1. The azo compounds represented by the foroga e in which X is one of agroup represented by the NHzZ I I 0 and on a.

wherein Q is a radical of the group consisting of straight and branched chain alkylene radicals having 1 to-10 carbons, mono-hydroxy-alkylene radicals having 3 to '7' carbons wherein the hydroxy group isattached to a carbon other than alkylene ether radicals having 1 to 4 carbonsin each alkylene group; R is at least one of the group consisting of hydrogen, alkyl having 1 to 6 carbons, "the corresponding 'alkoxy groups, halogen, carboxy and sulfonic acid and n is 1 to 4; each Y is one of a group consisting of radicals of amino-phenyl pyrazolones, amino benzenes, naphthylamines and 1- and 2-amino-naphtho1 sulfonic acids represented by the formulae and in which R" is from the group consisting of methyl and carboxyl; R is from the group con sistingof hydrogen, alkyl and alkoxy; n is 1 to 4; m is 1 to -2; R is one of a group consistingof hydrogen, alkyl, alkoxy and sulfonic acid; one

Z is hydroxy and the other is hydrogen; the Z' which is meta to hydroxy is sulfonic acid and the other is hydrogen; M is in the, 1- or 2-position of the naphthalene nucleus and is one of a group consisting of NEG N=NO0omcmcmomomoHmGNa and l NH,

wherein R. is one of a'group consistingof hydrogen, alkyl, alkoxy, halogen and sulfonic acid, and amino is in the meta or para position to "-00-; and each A is a radical of a metadihydroxy benzene represented by the formula 5 Lf I'he azo compound represented bythe qimq a j l V Y.

g 6. 'I'h' azo compound represented by-Qthe formula? f r '7. The formaldehyde complexes of the compounds of claim 1.

8. The formaldehyde complexes of the compounds of claim 2.

9. The formaldehyde complexes of the compounds of claim 3.

10. The formaldehyde'complexes of the compounds of claim 4.

11. The formaldehyde complexes of the compounds of claim 5.

12. The formaldehyde complexes of the compounds of claim 6.

13. The formaldehyde and metal complexes of the compounds of claim 1.

14. The formaldehyde and metal complexes of the compounds of claim 2.

15. The formaldehyde and metal complexes of the compounds of claim 3.

16. In the manufacture of a compound represented by the formula I in which X is one of a group represented by the formulae NH: 7 m aca y 'M wherein Q is a radical of the group consistin and of straight and branched chain alkylene radicals each Y is one of a group consisting of the radicals of amino-phenyl pyrazolones, amino benzenes, naphthylamines and 1- and Z-aminonaphthol sulfonic acids represented by the formulae and y {a i wherein R is one of a group consisting of hydrogen, alkyl, alkoxy, halogen and sulfonic acid, and amino is in the meta or para position to CO; and each A is a radical of a meta-dihydroxy benzene represented by the formula wherein R is one of a group consisting of hydrogen, alkyl'having 1 to 6 carbons, the corresponding alkoxygroups amino, halogen, CN, carboxyl and sulfonic acid; the steps which com-.

prise tetratizing a compound represented by X and coupling in alkaline medium with two molecular equivalents of a compound representedby Y, tetrazotizing the disazo product of said coupling and again coupling in alkaline medium with two molecular equivalents of a compound represented by A.

17. The process which comprises dyeing a dyeable fabric with a compound represented by the formula in which X is one of a group represented by the formula NE: NH:

wherein Q is a radical of the group consisting of straight and branched chain. alkylene radicals having 1 to 10 carbons, mono-hydroxy-alkylene radicals having 3 to '7 carbons whereinthe hydroxy group is attached to a carbon other than that directly attached to O- or S and. =alkylene ether radicals having 1 to4 carbons in each alkylene group; R is at least one of the (RI/I) NHz in which R is from the group consisting of methyl and carboxyl; R is from the group consisting of hydrogen, alkyl and alkoxy; n is 1 to 4; m is 1 to 2; R is one of a group consisting of hydrogen, alkyl, alkoxy and sulfonic acid; one Z is hydroxy and the other is: hydrogen; the Z and whichis meta to hydroxy is sulfonic acid and the other is hydrogen; M is in the 1- or 2-position of the naphthalene nucleus and is'one of a group consisting of 1's and I NHCO I wherein R is one of a group consisting of hydrogen, alkyl, alkoxy, halogen and sulfonic acid, and amino is in the meta or para position to -CO-; and each A is a radical of a meta-dihydroxy benzene represented by the formula wherein R is one of a group consisting of hydrogen,alkyl having 1 to 6 carbons, the corresponding alkoxy groups amino, halogen, CN, carboxyl and sulfonic acid; and then applying an aqueous solution of formaldehyde until a formaldehyde complex is formed.

SWANIE S. ROSSANDER. DONOVAN E. KVALNES. CHILES E. SPARKS.

. CERTIFICATE OF CORRECTION. Patent No. 2,2l .9,0l|.5. July 115, 19).;1.

SWANIE S. ROSSANDER, ET AL.

It is hereby certified that error appears in the printed specification of the above'numbered patent requiring correction as follows: Page 7, second column, line 69, claim 1, in the formula, for "(R v read -(Rv v and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the. case in the Patent Office.

Signed and sealed this 19th day of May, A. D. 1914.2.

Henry I Van Arsdale,

-('Sea1) Acting Commissioner of Patents. 

